Waterborne Coatings with an Emphasis on Synthetic Aspects: An

Chapter 1

Waterborne Coatings with an Emphasis on Synthetic Aspects: An Overview 1

Melissa A. Grunlan, Lin-Lin Xing, and J. Edward Glass

Downloaded by CORNELL UNIV on September 7, 2016 | http://pubs.acs.org Publication Date: April 1, 1997 | doi: 10.1021/bk-1997-0663.ch001

Department of Polymers and Coatings, North Dakota State University, Fargo, ND 58105

This chapter provides an overview of water-borne coatings to complement the chapters that follow. It provides the basic chemical reactions that many outside the field will not be familiar with, and general principles that those practicing in the field may have forgotten. The most active areas in water-borne coatings are in the synthesis of latices and water-reducible acrylics by a chain-growth polymerization mechanism and water-borne polyurethane, polyester, and epoxy resins synthesized by step-growth polymerizations. Water-borne epoxy resins are discussed in detail in chapter 5. The other resin families are discussed in this and in the chapter to follow. The emphasis in this chapter will address the synthetic aspects as imposed by the polymerization process on the stability of the disperse phases and their film properties.

Synthetic polymer coatings originally were applied from organic solvents. Solution viscosities, at a given concentration, are proportional to the polymer's molecular weight. Film properties, such as tensile strength and toughness also are proportional to the polymer's molecular weight. Therefore, to obtain the low viscosities needed for the application of a coating the concentration of the polymeric resin was necessarily low, and the organic solvent emitted to the atmosphere (VOC, Volatile Organic Component) was high. As society changed and environmental concerns were emphasized, coating technology has advanced in several directions. Two areas considered V O C free are U V cure(i) and powder(2) coatings. U V curing of solventfree formulations is restricted, with only a few exceptions, to flat surfaces, with film thickness and pigmentation limitations. Powder coatings are subject to Faraday effects and can not be applied to many surfaces. The effort to produce synthetic rubber during World War II led to the development of an emulsion polymerization process, and with it, water-bome coatings 1

Corresponding author

© 1997 American Chemical Society

Glass; Technology for Waterborne Coatings ACS Symposium Series; American Chemical Society: Washington, DC, 1997.

2

TECHNOLOGY FOR WATERBORNE COATINGS

as they are designed in the architectural and paper coatings area. Such an emulsion polymerization recipe employs a surfactant, a monomer with low solubility in water, and a redox free radical initiator in the aqueous phase (recipe given in Table I in chapter 2). When a monomer with low solubility in the aqueous phase (e.g., styrene and butadiene) is employed, the emulsion polymerization occurs by a micellar process. After the initiator has reacted with the monomer in the aqueous phase, the monomer propagates to an oligomeric form and then enters a micelle, formed by the aggregation of excess of surfactant used in the polymerization recipe. The chain growth polymerization (chapter 3 in reference 3) of the olefinic monomer then occurs in the micelle. When the chain growth polymerization of olefinic monomers occurs in bulk or solvent, the free-radical concentration of the propagating species should be kept below 10" molar to miriimize termination reactions. Polymerization in a micellar environment isolates the propagating species and permits higher concentrations of propagating radicals. Thus, higher rates of polymerization (Rp) with simultaneous higher molecular weights ( X , degree of polymerization) are realized, as described by the relationships (chapter 4 in reference 3) in equations 1 and 2.


8

n

3

Rp=10 Nnkp[M]/N where:

n = average number of radicals per micelle plus particle kp = propagation rate constant [M] = monomer concentration N A = Avogadro number X = r / r = Nk [M]/R n

where:

(1)

A

p

i

p

i

(2)

X = degree of polymerization r = rate of growth of a polymer chain rj = rate at which primary radicals enter the polymer particle N = steady state concentration of micelles plus particles k = propagation rate constant [M] = monomer concentration Ri = rate of initiation n

p

p

and 2/5

N = k(R / i) (a S) i

where:

t

3/5

s

(3)

k = constant | i = rate of volume increase of a polymer particle as = interfacial surface area occupied by a surfactant molecule S = total concentration of surfactant in the system

A more developed description of the process is given in chapter 2 by a major contributor to this technology, John Gardon. The high rates of polymerization, with



1. GRUNLAN ET AL.

Overview with an Emphasis on Synthetic Aspects

3

ease of removal of the heats of polymerization in an aqueous environment and the ease in handling of a low glass transition temperature particle, are major assets of the emulsion polymerization process. As the market was developed in the sixties, the compositions of the latices varied from styrene/butadiene, to methylmethacrylate/acrylic esters (for their exterior durability), to low cost vinyl esters. With the transition in latex compositions to vinyl acetate, the oligomers became more hydrophilic and participated less in the micellar polymerization process. They continued to polymerize in the aqueous phase and then aggregate into a polymer colloid. Consequently, the rate for an emulsion polymerization of vinyl acetate is not dependent on the surfactant concentrations as cited for styrene in equations 1 and 3. For a more detailed treatment of the nonmicellar emulsion polymerization where there is essentially no polymerization in micelles, (i.e., the Hansen, Ugelstad, Fitch, Tsai theory) the reader is referred to references 4 and 5. For a discussion of the influence of monomer and surfactant hydrophilicity on the median particle size and particle size distribution of the latex, the reader is referred to references 6 and 7, respectively. The use of seeding techniques to produce latices for more specialty applications is discussed in chapter 2. Compositional influences on interfacial tensions and how this affects the latex's morphology are discussed in chapter 3. What follows below in this chapter relates more to commodity latex production for use in architectural and paper coating markets. Surface Stabilizers In Latex Chain-Growth Synthesis The stabilities of latices in their early development were related to the electrostatic repulsions of particles due to catalyst fragments and adsorbed surfactants on their surfaces. Commercial materials demand more stability to electrolyte concentration, mechanical deformation and temperature variations than these entities can provide. Therefore, early in their development, the stabilities of latices were increased by oligomeric surface stabilizers, or by chemically grafted water-soluble polymer segments. These surface segments illustrated in Figure 1 provided electrosteric and steric stabilization. The most universal approach was the inclusion of methacrylic or acrylic acid in the latex synthesis recipe, generally in the second stage of a starved, semi-continuous process. The acids polymerize in sequence runs of acrylic or methacrylic acid, not possible in the step-growth synthesis of polyester and polyurethane disperse phases, discussed in the later section of this chapter. The repeating acid segments position near or on the surface of the latex and expand to provide electrosteric stabilization of the particle when neutralized. The parameters that influence the positioning of the acid surface stabilizers near the water/latex interface are the hydrophilicity of the copolymer and the latex's glass transition temperature^). Thus, for a methyl methacrylate latex having equivalent glass transition temperatures, the surface acid content and its extent of swelling (reflected by sedimentation coefficients in Figures 2 and 3) will be greater in a copolymer composition having a




4

more hydrophilic acrylate comonomer (where more is required of ethyl acetate than of butyl acrylate to achieve a given glass transition temperature, Figure 2). With the more hydrophobic acrylate comonomer, more of the 2 wt.% methacrylic acid charged is retained within the latex particle. The importance of the hydrophilicity of the latex composition also is evident in styrene and methyl methacrylate latices (not illustrated), both containing 50 % ethyl acrylate. The methacrylic acid segments are buried within the more hydrophobic styrene latex synthesized by a conventional batch process. In other compositions having a constant hydrophobicity but varying glass transition temperature, the importance of the glass transition temperature is evident (Figure 3). Such stabilizers have been important in small particle (100 nm) latices used in formulations containing a variety of pigments, because of their high pigment binding power. The importance of the oligomeric surface stabilizers in photographic processes are discussed in chapter 12. The theoretical treatment of the parameters influencing the stability of this type of latex particle and for those discussed in the next paragraph containing only nonionic grafted segments are treated in chapter 6 by Professor Goodwin.

C0 H 2

-C0" N H0 C "0 C 2

"O2C

2

2

7-

HO2C

Figure 1. Electrosteric and Steric Stabilized Latices While oligomeric surface acid stabilizers are used in vinyl acetate latices in the paper coatings area, where water sensitivity is not a factor in formulations containing high clay contents, and in methacrylic and styrene based latices in architectural latex coatings, vinyl acetate latices in low pigment volume concentration architectural coatings are water sensitive and surface acids are not the method of


1. GRUNLAN ET AL.


5

1.9 1.7 ^1.5 CO 1.3


1.1 0.9 3

4

5

6

7

8

9

10

11 12

pH Figure 2. Expansion of acrylic copolymer latexes bearing 2% acid. So / S (relative rate sedimentation of particle) verses dispersion pH. M M A / M A IB A : methyl methacrylate / ethyl acrylate / butyl acrylate. • M M A / E A / B A , 40/52/6, Tg 15°C; O M M A / E A / B A , 40/58/0, Tg 18°C; A M M A / E A / B A , 49/0/49, Tg 15°C (Adapted from ref. 8.).

1.4 1.3 1.2 SOU OT 1 0.9 0.8 0.7 3

4

5

6

7

8

9

10 11 12 13

PH Figure 3. Expansion of Butyl Acrylate/methyl Methacrylate Copolymer Acid Bearing 2% Latexes. So/S (relative rate of Sedimentation of Particle) verses Dispersion pH. * 50/50, Tgl5°C; O 37.5/62.5, Tg 33°C; A 31/69, Tg 44°C; • 25/75, Tg 54°C; 0 0/100, Tg 105°C (Adapted from ref. 8.).


6


stabilization. A n alternative approach with the more hydrophilic vinyl ester monomers is to chemically graft segments of water-soluble polymers to the growing polymer chain. Generally, cellulose ethers are used in the synthesis of vinyl acetate latices for architectural coatings; vinyl acetate/vinyl alcohol copolymers are grafted to latices used in adhesive applications. Grafting of the nonionic stabilizers to the latex surface also provided a means of increasing viscosities at high shear rates (10 s" ) for vinyl acetate latices, and there was a desire to impart this to large particle size acrylic latices. The general technical understanding of die sixties impeded this development on a wide commercial scale. It was known that the vinyl acetate radical was high in energy and therefore responsible for the grafting of polyvinyl acetate) to the cellulose ether. Efforts by most to graft acrylics or styrene to cellulose ethers were unsuccessful and this was generally considered to be related to the lower energy of these propagating radicals. In fact, the lowest energy radicals in these systems were those generated at the carbon acetal linkage of the cellulose derivative or next to the carbonyl group of the acetate segments of the vinyl alcohol copolymer (Figure 4). The primary deterrent to the commercial production of methacrylic latices was the relatively uninterrupted propagation of the methacrylate radical without transfer reactions. The high energy vinyl acetate radical transferred with everything in the system except water, and there was therefore, sufficient water-soluble polymer chemically grafted to ensure adequate stability of the final vinyl acetate latex. Once the error in understanding of the mechanism was understood (9), water-soluble chain transfer agents, such as triethanolamine, were added to the polymerization recipe and methyl methacrylate latices, with sufficient cellulose ether grafts for stability, were successfully prepared. During this period, polymer dispersions also were prepared in organic solvents using a different steric stabilizer technique. These Non-Aqueous Dispersions (70) of course contained VOC's of now unacceptable levels. Both these and the water-borne


4

CH OH 2

1

-^CH CH-CH CH-^2

H O ^ ^

2

O OH

4

4 *

i

O I CH,

Figure 4. Low Energy Radicals Generated on Cellulose Derivative and Vinyl Alcohol Copolymer.


1. GRUNLAN ET AL.


7

latices discussed above must coalesce to form a continuous film, and to do so with sufficiently high glass transition temperature latices to provide reasonable film durability after application, requires a coalescing aid. This contributes to the V O C of aqueous disperse phase coatings and will be addressed in chapter 4.


Disperse Phases in Original Equipment Manufacturing Coatings Latex coatings used in the paper and architectural coating areas are thermoplastic. Coatings for industrial markets, as in automotive and appliances, require more durability, generally in a more hostile environment. The harder surface of a crosslinked thermoset film is required. The approach to achieving a low V O C coatings in this area has been the "high solids" route. Oligomers in the 3,000 to 5,000 molecular weight range are prepared. The synthesis of such resins is considered first in this chapter, to understand how the synthesis influences their conversion to aqueous dispersions and the stability of the particles generated. Examples of their preparation by step-growth synthesis are given in Scheme 1 for the preparation of polyesters (1A), noted for their low costs and flexibility; for epoxies(lB), noted for their solvent resistance and adhesion; and for urethanes(lC), noted for their abrasion resistance and flexibility. The chain growth synthesis of methyl methacrylate oligomers, noted for their durability, containing 2-hydroxyethyl methacrylate units randomly placed within the chain are illustrated in Scheme ID. The reactive groups from these synthesis are generally hydroxyl units that are crosslinked with multifunctional compounds such as melamine or the isocyanate groups of an isocyanurate compound (Scheme 2). Examples of such reactions are illustrated in Scheme 2 between a polyester with terminal hydroxyls and a melamine resin (2A), between a methyl methacrylate chain containing multiple hydroxyl units and the isocyanate units of an isocyanurate (2B), and between an epoxy and an acid terminated polyester (2C) or with amine functionalities (not illustrated). Group Placement in Chain-Growth Oligomers. Methyl methacrylate oligomers (i.e., o-MMA, "water-reducible (W-R) acrylics") are used in O E M applications for their proven durability. They differ from an architectural latex formulation in that these oligomers contain 2-hydroxyethyl methacrylate (HEMA) or acrylate (HEA) units, 7 wt.% or less, that provide the crosslinking sites through their hydroxyl units (Scheme ID). They also contain acrylic acid units (not illustrated) to provide electrosteric stability to the particles produced on the introduction of water. W-R acrylics also differ in that they generally do not contain traditional surfactants. Methacrylic acid is generally used in the synthesis of acrylic latices because a significant amount of watersoluble poly(acrylic acid) would be formed and reside in the aqueous phase. W-R acrylics are synthesized in an organic media and the lower cost acrylic acid is used. There has been considerable discussion about the desirability of uniform crosslink density networks in O E M films (Figure 5). This is difficult to obtain in a free-radical,



o

r

2

4

/

2

CH =C

3

3

+

OCH

V°

CH

2

o

) 2

2

(n)CH -C

2

N

3

2

2

R-

OCH CH OH

CH

2

"I — ^ — O CH CHCH O OH

(n) O C N — R — N C O

3

n

2

3

5

) 2

— ^

C

• ° - ^

C

2

H

+

^

OC H CH-C H

0

^- (n+2)HCl

2

2

H

2

R—CH C

OCH3

3

2

2

2

2

/ OCH3

3

CH -CH C\ c=o OCH CH OH

3

QH -CH Cc=o c=o CH

^-R-OCONH—R-NHCO—O-^—R—

^ ^ — C ( C H

HO

3

v

JJQ—CCH4-0— ? - ( C H ) ? '4

+ ( + 1) H O — < ^ > — C ( C H ) - < ^ > — O H

C ( C H

2

tin catalyst^ 180 C

QH

3

2

2

c k OCH CH OH

c Hija-

Scheme 1. Preparation o f Oligomers in the 3,000 to 5,000 M o l e c u l a r Weight Range (A) Polyester (B) E p o x y (C) Urethanes (D) Methylmethacrylate with 2-Hydroxyethyl Methacrylate Units.

(9n)

D.

ChailLiGrowth

+

—

o

II + (n)HO-(5-(CH )4-C-OH

(n+2)CH -CH-CH Cl

2

C H P C H - -0 —

+

(n l)HO-(CH ) -OH

(n+l)HO~R-OH

C.

B.

A.


I

00



1. GRUNLAN ET AL.


9






1. GRUNIAN ET AL.


11


12


chain-growth oligomerization. The inclusion of the hydroxy containing monomer in a given oligomeric chain is dependent on the monomer's relative reactivity ratio and concentration (chapter 5 in reference 3). Thus, in a low molecular weight chain, a H E M A or H E A unit may not be incorporated in many methacrylate oligomers and many chains may have more than two hydroxy containing H E M A or H E A units. In addition, there is a very low probability that hydroxyl units would be positioned at the terminal positions of the methacrylate chains, considered important to the formation of a uniform network structure on curing with multifunctional crosslinkers. To this latter goal,researchersdeveloped an anionic initiator ( i i ) , a ketene silyl acetal, that affected the synthesis of a monodisperse molecular weight o-MMA resin, typical of an anionic initiator, but also with the ability to place hydroxyl group at both ends of the chain. Cost is the primary parameter in coating formulations, and this innovative approach has not achieved a dominant commercial position.

Figure 5. Uniform and Non-uniform Crosslink Density Networks.

Water-reducible acrylics, used in thermosetting applications, are prepared in an organic solvent (such as t-butanol) and "reduced" to an aqueous disperse phase by dilution with water. This type of resin was at one time the primary resin used in automotive coatings, but they were humidity sensitive and this caused major problems during production. The data in Figure 6A illustrates the influence of dilution of such a resin with t-butanol, the solvent used in synthesizing the low molecular weight W-R acrylic, and with water on the solution or dispersion viscosity. The dilution of a traditional, high molecular weight acrylic latex with water also is illustrated. In two of the curves, the viscosity decreases with dilution, as would be expected; however, with water addition of the t-butanol acrylic resin solution abnormal viscosity behavior is observed. Initially the viscosity decreases due to dilution; however, with continued dilution the viscosity increases. The addition of water to the t-butanol W-R acrylic solution causes a phase inversion and it is in this area that a viscosity abnormality occurs (Figure 6A). The magnitude of the viscosity abnormality at an intermediate dilution level is dependent on the molecular weight of the W-R acrylic, on the monomer acid level in the resin (72, 13) (Figure 6B), and on the extent of neutralization. Prior to dilution of the ca. 70 wt.% resin in butanol the acrylic acid segments are partially neutralized with an amine such as 2-


1. GRUNLAN ET AL.


13


(dimethylarnino)ethanol(DMAE). The abnormality arises in part from the decreasing ratio of solvent to water, causing the nonpolar segments of the resin to associate. The solvent is soluble in the resin and some of it swells the aggregates formed on dilution of the t-butanol with water. The swollen aggregates increase in number with continued dilution and the viscosity increases with increasing volume fraction as would be expected from the principles defined by the Mooney (14) or Kreiger-Dougherty (75) equations (discussed in chapter 6 of this text). With increasing water dilution the occluded solvent distributes more to the continuous water phase and the aggregates begin to shrink in size. This complements the dilution effect and the viscosity begins to decrease again. A similar aggregation phenomenon has been reported in aqueous polyester dispersions (76). 1

1

i

1

f \

| i

10000

Water 1000

t-Bulyl alcohol

/ /

a £

100

/ I I / I / I / / / / /

'

/

/

/

/

/

/

/

Latex

j

-

/

/

i 10

'

70

1 30

1 «0

50

60

Polymer Concentration [%]

Figure 6A. Viscosity dependence on polymer concentration for a latex and for water and t-butyl alcohol solutions of a 10/90 acrylic acid/butyl methacrylate copolymer with 75% effective neutralization with dimethylaminoethanol (Reproduced with permission from ref. 12).


14


1 1 1 '1 50/50 acrylic acid/butyl methacrylate 10000 __ copolymer ratio J

"

/ 30/70

// / c E

1000

t I

1 /


/ 20/80

o u

: 100

10

10

1

20

1 30

/

10/90

l 40

Polymer Concentration [•/•] !

Figure 6B. Viscosity dependence on polymer concentration for dilutions in water of acrylic acid butyl methacrylate with different copolymer ratios and 75% effective neutralization with dimeylaminoethanol (Reproduced with permission from ref. 12).

The viscosity abnormality disappears as the acid content of the resin is increased (Figure 6B). As the acid percentages in the resin is increased, fewer of the acid monomer units are isolated and trapped in the aggregated resin's interior, where with their solvation by water and reaction with the solubilized base, they help swell the particle. Interestingly, it has been observed in studies at NDSU that approximately 25 % of the acid monomer is trapped within the acrylic disperse phase in both methacrylate latices and in water-reducible acrylics. The surface acid units in W-R acrylics are not desirable crosslinking sites with multifunctional isocyanates and melamine resins. The reaction of isocyanates with carboxylic acids leads to carbon dioxide liberation and possible film defects. A reaction with melamine lead to ester linkages and possible hydrolysis during the life of the film. Reaction of the latter with the hydroxyl of the H E M A units leads to stable ether crosslinks. The goal is to minimize the number of carboxylate groups as far as particle stability in the aqueous


1. GRUNLAN ET AL.


15


phase will permit and to maximize the number of hydroxyl groups of the H E M A or H E A units for crosslinking sites. There is a second problem to be addressed in these resins. The melamine crosslinking reactions are inhibited by the amine used to neutralize the carboxylate groups. This can lead to poor surface gloss when the monomers in the surface, where an amine of low volatility may evaporate, can polymerize without polymerization occurring throughout the film where amine is still present. The resulting immobilized surface film wrinkles forming an irregular surface when the subsurface, later free of amine by evaporation, polymerizes, and shrinks. Group Placement in Step-Growth Synthesis. The majority of polymers used in O E M applications arise from step-growth polymerizations (chapter 2 in reference 3). There are disadvantages and advantages to a step-growth polymerization. The most notable disadvantages are the broad molecular weight distributions (illustrated for isocyanate reaction products (17) in Figure 7), and high molecular weights are not obtained until high conversions are reached. Lower molecular weights can be volatile and are toxic, especially isocyanates. The broad distribution in molecular weights is a concern if the viscosity of the resins is important. The distribution is not a primary concern if the polymers are taken to high conversion and molecular weight, but the latter is generally not the case for the resins used in thermosetting applications. A n advantage in a stepgrowth polymerization, to some extent countering the broad molecular weight distribution, is that by controlling the stoichiometry, the functional groups (i.e., hydroxyl, isocyanate, epoxy, or carboxylate groups) can be placed in the terminal position (Scheme 1), prior to crosslinking to the thermoset coating. In the production of aqueous polyester dispersions, high reaction temperatures are required for polyesterification (>180 °C). This restricts the wide use of "flexible components" such as poly(tetramethylene oxide) in polyesters. The sulfonate anion (Figure 8B) promotes charge stabilization across a broad pH range (18) and the structure given in 8B is the anionic stabilizer used in commercial polyesters. The hydrolytic stability of aqueous polyester dispersions are addressed in this book. Epoxy resins are covered in chapter 5. The systems most discussed in the open literature are water-borne methanes. Polyurethanes are formed by the reaction of diisocyanates with diols (19, Scheme 1C), but in processing and application, many more isocyanate reactions can be involved. They are given in Scheme 3. The reaction of an isocyanate with an alcohol unit provides the desired urethane linkage (3A), reaction with a carboxylate group (3B) leads to a carbamic acid intermediate that decomposes to carbon dioxide and to an amine, that can react with other isocyanate in the system to form urea linkages(3C). The liberation of C 0 in a coating system can lead to surface defects and is undesirable. Recent studies indicate that the rate of CO2 production during the urethane network formation can be controlled by crosslinking conditions (20). The reaction of an isocyanate with water is illustrated in 3D. It also should be mentioned that because both urethane and urea linkages still have an active hydrogen, they can further react 2





1. GRUN1AN ET AL.


17

A. Reaction with Alcohols: most widely used in coatings

R_N=C=0

+ R — O -- H

-

"*

R-N-iH

urethane R Reaction with Carboxylic Adds : Polyols (especially polyesters) must have low acid content O O ~ ^ R—N-C—O-C—R 11


R-N=C=0

+ R—COOH

11

R-N-C—R' + CO2

i

H

H

amide C. Reaction with Amines : fast reaction limits use O R_N=C=0

+

R—NH

R—N-C—O — N - R '

2

b

H

D. Reaction with Water: water should be removed from polyols

R_N=C=0

+

H2O

-

R-NJLO-H

*

R - N H 2 + CO2

H

E Reaction with urethanes

f R— N = C = 0

+

?f

f

R—O—C—N—R

NH—R

1

R —O—C—N—R

aUophanate F. Reaction with Urea

If R—N=C=0

R—N—C—N—R' H

H

R—N—C—N—K 0 = H H—N—R ?

biuret

Scheme 3. Reactions of isocyanate with (A) alcohol (B) carboxylate ( Q amine (D) water (E) urethane (F) urea



18


with an isocyanate to form an allophonate (3E) and a biuret (3F), respectively. However, these products typically are only formed in baked, uncatalyzed systems. The methodology of producing an aqueous disperse polyurethane phase (PUDs)(27), which can generically represent the step-growth synthesis of O E M type resins, is given in Schemes 4 - 6 . First, a medium molecular weight isocyanate terminated prepolymer is formed by reacting a diol with a stoichiometric excess of diisocyanate (27, Scheme 4). The second step is to chain extend this prepolymer, where problems in viscosity build up and the fast rate of reaction of the isocyanate units with the amine groups are encountered, and methodologies then vary with the process used. They include a solvent process using acetone (Scheme 5), a ketimine/ ketazine process (Scheme 6), a prepolymer mixing process, and a hot melt process. The latter processes employ technologies that reduce or eliminate the use of organic solvents. In the acetone solvent process (27) the prepolymer is chain extended with a sulfonate based diamine, to give the desired high molecular weight (Scheme 5). Acetone prevents excessive viscosity build up. Water is then added to the polymer solution until water becomes the continuous phase. Viscosity abnormalities such as those reported with water-reducible acrylics have not been detailed. The solvent is removed by distillation, adding to production costs, to obtain dispersions low in V O C . The ionic sulfonate group acts as a charge-repulsion stabilizer. Although this process yields reproducible P U dispersions, it is limited to those that are soluble in acetone, and consequently, the resulting urethane films are not very solvent resistant. One of the alternatives to the solvent process is the Ketimine/Ketazine process. It does not require distilling off a solvent or high shear equipment; the molecular weight builds in water so a viscosity build up is avoided and the solvent resistance of the final film can approach that cast from solvent. The reactions are given in Scheme 6. This process, however, is sensitive, and subject to product variations. Surface Stabilizers in Step-Growth Polymerizations Like traditional latices, "water-reducible, step-growth polymers" require anionic and/or nonionic surface stabilizers to maintain dispersion stability at reasonable volume solids in a coating formulation. This is accomplished in step-growth polymers by the inclusion of a carboxylate (Figure 8A), sulfonate (8B), or nonionic oxyethylene (8C) group, placed within the chain by a diol or diamine structure (illustrated in Schemes 4 and 5). These disperse phases are not as stable as the acrylic disperse phases, for the surface stabilizera are isolated as one charge and there is no steric contribution with these isolated anionic groups. They do not occur in sequence runs as observed in chaingrowth acrylic polymers, and therefore, the particles are more susceptible to flocculation by mechanical and thermal forces and by electrolyte concentrations. There is also a particle size distribution difference among these different disperse phases, with the W-R acrylic being much smaller than those obtained from an emulsion polymerization.


1. GRUNLAN ET AL.

Overview with an Emphasis on Synthetic Aspects CH

2n H O - O H

3

+ n HOCH —i-CH OH 2

+ 4n OCN—R—NCO

2

ÔOH

1 O

O

O

CH

O

3

0

0

OCN-R—N&O-K^N-R-NftoCH^^H o}!:>r-R~Nl!:0-^l!:N---R--NCO 2

k

k

(tooH

k

k

k

k

|NR Downloaded by CORNELL UNIV on September 7, 2016 | http://pubs.acs.org Publication Date: April 1, 1997 | doi: 10.1021/bk-1997-0663.ch001

3

O

O

O

CH

3

OCN-R-NÔ-O&Nr-R-NÔCH^—CH OCN-R-NCO-OCN-R-NCO 2

k

k

k

(too" NHRJ I

l.Bfl

j 2. OH-fimctional Chain Terminator Hydroxy-functbnal Dispersion Scheme 4. Prepolymer Process: Preparation of hydroxy-fimctional dispersion.

When an acrylic latex is thickened with a nonadsorbing polymer such as hydroxyethyl cellulose, the latex will flocculate by a depletion flocculation mechanism (discussed in detail in chapter 6). This is usually not observed visually. With a stepgrowth disperse phase, separation is observed within hours(22). This does not happen when the thickener is a Hydrophobically-modified, Ethoxylated URethane (HEUR) polymer. HEUR polymers have been discussed in detail with respect to their synthesis, solution behavior and structural influences on architectural coatings rheology (23, chapters 10,17, and 24, respectively). The adsorption of an HEUR thickener on a latex is determined by its chemical composition (that defines the energy of the surface), the concentration of surface acids and the amount of surfactant present (24). The molecular weight, concentration and effective hydrophobe terminal size on the HEUR are also important. The relative concentration and size of the surfactant and of the effective hydrophobe terminal size of the HEUR are the key variables in the adsorption process. There is no free surfactant used in the synthesis of a step-growth disperse phase, and therefore no impedance to adsorption and stabilization.


19

20


o

o

OCN-R-NH—C—O

+ H2N-CH2-CH2-NH

"O—
il^-CH2-S03Na

1

acetone

0

0

-O—(!:—N -R—N


H

O

O

—C—N -CH2-CH2-N—(H—N-R—N—C-

A A

d:H

2

H

A

S0 Na 3

water

Dispersion of Polyurcthane-urca in Water/Acetone

acetone removal

Aqueous Dispersion of Polyurethane-urca

Scheme 5. Acetone Process: Preparation of Aqueous Dipsersion of Poryurethane-Urea.

As noted earlier, the broad molecular weight distribution in step-growth oligomers is off-set by the ability to place the reactive groups in the terminal position. As noted in the preceding paragraph, the greater instability of step-growth dispersions can be improved by steric stabilization through adsorption of HEUR associative thickeners. By changing R and R' in Scheme 1, it is possible to vary the crosslinking, chain flexibility, and intermolecular forces among the chains. It has been well documented (25) that increasing the stiffness of the mainchain will increase the modulus or glass transition temperature of a polymer and suppress secondary transitions responsible for impact strength and flexibility in a polymer. The most unique aspect of step-growth polymers is the latitude in designing hardness and flexibility into the resin, discussed below, in an academic example. More practical approaches are discussed in chapter 9.


1. GRUNLAN ET AL.


0

0

O C N — R — N H C O ~ ^

C H

21

0

3

O!!:NI^-R—NCHO-CH -
2

io" HNR 2

3

Hydrophflic Isocyanate Terminated Prepolymer + Ketimine/Ketazine

N

C=N—R'"-N=C.

Water

o n /

\C=0


2

\J

W

\J

it

+ H N—R"-NH 2

\J

\J

2

\J

ôfeNH—R—NIllllNH—R'-NrllflNH—R—Nllfco—CH -C—CHz-O&NH—R—NHÔ""** 2

io

2

HNR

3

Aqueous Dispersion of Polyurethane-Urea

Scheme 6. Ketimine/KetazineProcess: Preparation of aqueous dispersion of polyurethane-urea.

Influence of Phase Transitions on Film Properties Designing hardness and flexibility in an applied film is accomplished by varying the carbon structure between the difunctional units, and it is best demonstrated in the open literature with polyurethanes(PUs). The oligomeric diol carrying the low glass transition temperature segments can be represented by polycaprolactonediol, polyesterdiols or poly(tetramethylene oxide)diols (PTMO). Urethane linkages to aromatic segments are unstable in sunlight and in alkaline aqueous media; therefore, the diisocyanates used in coatings are aliphatic. The diisocyanates represent the hard segments with high glass or melting transition temperatures. Due to the difference in polarity of the segments the PUs exhibit a phase separated morphology with distinct hard and soft segment domains. The good mechanical properties (e.g., stiffness with flexibility) of PUs have been attributed to this phase separation at temperatures between the transition temperatures of the soft and hard segments. In addition, PUs aqueous dispersions (PUDs) have the ionic stabilizers needed for disperse phase stability, that in the final film can result in coulombic forces of attraction (as they do in ionomers (26)). These columbic forces between ionic centers are claimed (27) to enhance the mechanical properties of PUD films over the conventional thermoplastic PUs. The ionic group attractions complement hydrogen bonding among the urethane and urea groups (attributed to result in the excellent abrasion resistance of PUs) to achieve unique film properties. These types of systems in real coatings will be discussed in chapter 9. This chapter will close with an example that delineates the


22


HO-^^-CH^-OH

H ^ - O I ^ r

1

^

H^-OTj^jH-ttHj

CHj-CHj-COjNa

ioOH

00OH

B H^-CHj-CH^NH SO3iNa

CHj-CH^-SQjNa

SQsNa


GOOH

Na+

Of

5-suIfo)isophthaic acid (5-SSIPA)

OCN - ^ C H ^ N - C O - N H - f C H ^ N C O

%

4

NH " f C H ^ N H - C O -0-{CH^CH^))-R

J.

ho I«I-(CH^NH-CO-0-(CH2CH203hR

Figure 8. Surface stabilizers. (A) carboxylate (B) sulfonate (C) nonionic oxyethylene groups. latitude in properties that can be obtained with changes in the synthesis component ratios. The following materials (28) highlight the latitude in film properties that can be achieved in a step-growth polymer. The polymers synthesized are illustrated in (Figure 9A). The simplest way to achieve phase separation of the hard segments is to increase the amount of these units; however, too high a concentration of hard units can embrittle the film. In the materials illustrated in Figure 9A, the hydrophilicity and ability to crosslink are accomplished through pyridine (BIN) units in the hard segment that are reacted with iodopropane (IP, to increase the hydrophobicity of the hard segment) or diiodopropane (DIP, to increase crosslinking among the hard segments). The hard segment concentration was varied: 41, 52 and 62 wt.%, and their tensile properties are illustrated in Figure 9B. The materials containing the broadest spectrum of properties


1. GRUNLAN ET AL.


23


obtainable are best illustrated in the 54 wt.% hard segment materials. PTMO in these studies is poly(tetramethylene oxide). Their dynamic mechanical properties are illustrated in Figure 10. The glass transition temperature of the soft segment decreases, as the alkyl group is attached to the pyridine ring, suggesting that the alkyl group improves the phase separation and thereby provides a purer soft segment. The -130° C peak is associated with the crankshaft transition of the four methylene units (25), contributing to impact strength; the transition near -50°C is the glass transition temperature of the polyether (PTMO). The dihalide crosslinks two pyridine groups giving a broad rubbery plateau transition in the plus 100° C temperature range. These types of transitions are not easily inserted in chain-growth polymers, and provide an architectural scenario to fine-tune film properties in step-growth polymers.

Figure 9A. PTMO-MDI-BIN.

B4HP B54IP B68IP

B54 H68

B4IDIP B54DIP B68D1P

CiO

/

0

u

200

400

600

Strain (%) Figure 9B. Tensile properties of materials illustrated in Figure 9 A .


800

24


1E+10

1E+2

-IE+1

-IE+0

«>


c

1E+1 -150 -100

B54 V B54IP BS4DIP -50

0

SO

100

150

200

- IE-1

1E-2 250

Temperature (°C) Figure 10. Dynamic mechanical properties of materials illustrated in Figure 9A.

Conclusions The general principles associated with the synthesis of organic binders and the stability of their aqueous disperse phases are reviewed in this chapter. For application in commodity architectural and paper coatings areas, oligomeric surface structures are required. This is achieved by copolymerizing sequence runs of oligomeric acid or by grafting water-soluble polymers to the binder during the synthesis of the emulsion polymer. The procedures utilized to achieve this goal for different monomers are described in this chapter. Modification and development of different latex surface morphologies are discussed in the two chapters that follow. More durable coatings are required in industrial applications and this is accomplished after application by crosslinking (he applied oligomers to thermoset resins, and the approach to resin synthesis and dispersion stability, prior to application, is more complex. The majority of polymers used as thermosets arise from step-growth polymerizations, that have disadvantages and advantages relative to chain growth polymers. The most notable disadvantages are the broad molecular weight distributions and the volatility and toxicity of lower molecular weights, especially isocyanates. The broad distribution in molecular weights is a concern if the viscosity of the resins is important. The isolation of the acid stabilizing moieties in a step-growth synthesis also produces a more unstable dispersion, but this can be compensated for by using hydrophobe-modified, ethoxylated urethane thickeners that provide steric stabilization through adsorption on the surfaces of step-growth polymer disperse phases.


1. GRUNLAN ET AL.


25

An advantage of a step-growth polymer, to a large extent countering their disadvantages, is that by controlling the stoichiometry the functional groups (e.g., hydroxyl, isocyanate, epoxy, or carboxylate groups) can be placed in the terminal position, prior to crosslinking the oligomers to a thermoset coating. Another advantage is that chain flexibility and intermolecular forces can be designed into the resin to provide high and low temperature transitions. This is the most unique aspect of stepgrowth polymers. These types of transitions are not easily inserted into chain-growth polymers, and they provide an synthesis scenario to fine-tune film properties, such as hardness and flexibility, into step-growth polymers.


Literature Cited 1. Hoyle, C.E.; Kinstle, J.F., Eds., Radiation Curing of Polymeric Materials; A C S Symposium Series 417, American Chemical Society: Washington, DC, 1990. 2. Jilek, J.H., Powder Coatings; Federation of Societies for Coatings Technology: Blue Bell, PA, 1991. 3. Odian, G., Eds., Principles of Polymerization; 3rd Edition, John Wiley & Sons, Inc.: New York, 1991, Chapter 4. 4. Fitch, R.M.; Tsai, C.H. in Polymer Colloids; Fitch, R.M., Ed.; Plenum press; 1971; pp.73 and pp.103. 5. Hansen, F.K., in Polymer Latexes: Preparation, Characterization, and Application, ACS Symposium Series 492, Daniels, E.S.; Sudol, E.D.; El-Aasser, M.S.; Eds., American Chemical Society, Washington, DC, 1992; Chapter 2. 6. Yeliseyeva, V.I., in Emulsion Polymerization, Pirma, I., Ed., Academic Press, New York, 1982; Chapter 7. 7. Dunn, A.S., in Emulsion Polymerization, Pirma, I., Ed., Academic Press, New York, 1982; Chapter 6, and in Polymer Latexes: Preparation, Characterization, and Application, ACS Symposium Series 492, Daniels, E.S.; Sudol, E.D.; El-Aasser, M.S.; Eds., American Chemical Society, Washington, DC, 1992; Chapter 4. 8. Hoy, K.L., Journal of Coatings Technology, 1979, 51 (651), 27. 9. Craig, D.H., in Water-Soluble Polymers: Beauty with Performance, Advances in Chemistry Series 213, Glass, J.E., Ed., American Chemical Society, Washington, D C , 1986; Chapter 18. Several additional studies were reported in ACS-PMSE national meeting reprints after this publication and the study was later republished in J. Coatings Techn. 10. Barrett, K . E . J., Ed., Dispersion Polymerization in Organic Media, Wiley, London, 1975. 11. Webster, O.W., Sogah, D.Y., in Comprehensive Polymer Science, Eastman, G.C.; Ledwith, A.; Russo, S.; Sigwalt, P., Eds., Pergamon Press, N Y , 1989; Chapter 10. 12. Richards, B . M . ; Masters Thesis, North Dakota State University, Fargo, ND, 1977. 13. Brandenburger, L.B.; Ph.D. Thesis, North Dakota State University, 1977. 14. Mooney, M.; J. Polym.Sci., 1959, 34, 599.



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15. Krieger, I.M., Adv. Colloid and Interface Sci., 1972, 3, 111. 16. Raynolds, P.W., Proceedings of Water-borne and Higher Solids Coatings Symposium, 1990, New Orleans, L A , pp. 121-129. 17. Thompson, C.M.; Taylor, S.G.; McGee, W.M.; J.Polym. Sci. Part A; Polym. Chem. 1990, 28, 333. 18. Kuo, T.; Blount, W.W.; Moody, K . M . ; Proc. ACS Div. Polymer Materials: Science and Engineering, 1992, 66, 168-169. 19. Dieterich, D., Progress in Organic Coatings, 1981, 9, 281. 20. Potter, T.A.; Rosthauser, J.W.; Schmelzer, H.G., Proceedings of Water-borne and Higher Solids Coatings Symposium, 1986, New Orleans, L A , pp. 162-165. 21. Rosthauser, J.W.; Nachtkamp, K., "Water-borne Polyurethanes," K . C . Frisch; Klempner, D.; Eds., Advances in Urethane Technology, 1987, 10, 121. 22. Kaczmarski, J.P.; Fernando, R.H.; Glass, J.E.; Journal of Coatings Technology, 1993, 65 (818), 39. 23. Wetzel, W.H.; Chen, Mao; Tarng, M.R.; Kaczmarski, J.P.; Lundberg, D.J.; Ma. Zeying; Alahapperuna, K. and Glass, J.E.; in Hydrophillic Polymers: Performance with Environmental Acceptability, Advances in Chemistry Series 248, Glass, J.E., Ed., American Chemical Society, Washington, DC, 1996. Chapters 10, 17, 24. 24. Ma, Z.; Chen, M. and Glass, J.E.; Colloids and Surfaces, 1996, 112, 163. 25. Heijboer, J.; Brit. Poly. J., 1969, 1, 3. 26. Lundberg, R.D.; Encyclopedia of Chemical Technology, Supplement Vol., John Wiley & Sons, Inc. 1984, p. 546. 27. Yang, W.P., Proc. ACS Div. Polymer Materials: Science and Engin. 1992, 66, 216. 28. Velankar, S; Yang, C.Z.; Couper, S.L.; Polymer Preprints, 1996, 37(1), 400.


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